Richard Anthony DiPietro

Degradation and failure of MEH‐PPV light‐emitting diodes

Light‐emitting diodes made with poly(2‐methoxy‐5(2′‐ethyl)hexoxy‐phenylenevinylene) (MEH‐ PPV) using indium‐tin‐oxide (ITO) as anode and Ca as cathode have been examined as they age during operation in a dry inert atmosphere. Two primary modes of degradation are identified. First, oxidation of the polymer leads to the formation of aromatic aldehyde, i.e., carbonyl which quenches the fluorescence. The concomitant chain scission results in reduced carrier mobility. ITO is identified as a likely source of oxygen. The second process involves the formation of localized electrical shorts which do not necessarily cause immediate complete failure because they can be isolated by self‐induced melting of the surrounding cathode metal. We have not identified the origin of the shorts, but once they are initiated, thermal runaway appears to accelerate their development. The ultimate failure of many MEH‐PPV devices occurs when the regions of damaged cathode start to coalesce.

Probe-based ultrahigh-density storage technology

Ultrahigh storage densities can be achieved by using a thermomechanical scanning-probe-based data-storage approach to write, read back, and erase data in very thin polymer films. High data rates are achieved by parallel operation of large two-dimensional arrays of cantilevers that can be batch fabricated by silicon-surface micromachining techniques. The very high precision required to navigate the storage medium relative to the array of probes is achieved by microelectromechanical system (MEMS)- based x and y actuators. The ultrahigh storage densities offered by probe-storage devices pose a significant challenge in terms of both control design for nanoscale positioning and read-channel design for reliable signal detection. Moreover, the high parallelism necessitates new dataflow architectures to ensure high performance and reliability of the system. In this paper, we present a small-scale prototype system of a storage device that we built based on scanning-probe technology. Experimental results of multiple sectors, recorded using multiple levers at 840 Gb/in2 and read back without errors, demonstrate the functionality of the prototype system. This is the first time a scanning-probe recording technology has reached this level of technical maturity, demonstrating the joint operation of all building blocks of a storage device.

The Use of Styrenic Copolymers To Generate Polyimide Nanofoams

New routes for the synthesis of high T-g thermally stable polymer foams with pore sizes in the nanometre regime have been developed. Foams were prepared by casting well-defined microphase-separated block copolymers comprising a thermally stable block and a thermally labile material. At properly designed volume fractions, the morphology provides a matrix of the thermally stable material with the thermally labile material as the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis generating pores, the size and shape of which are dictated by the initial copolymer morphology. Several labile blocks were surveyed including polystyrene, poly(alpha-methylstyrene) and several alpha-methylstyrene/styrene copolymers. Each of these polymers can unzip to its monomer upon heating; however, the rate is substantially slower for polystyrene. The copolymers were synthesized through either the poly(amic acid) precursor, followed by chemical imidization to the polyimide form, or the poly(amic alkyl ester) precursor followed by thermal imidization. The decomposition of the labile coblock was studied by thermogravimetric and dynamic mechanical analysis. Upon decomposition, the foams showed pore sizes in the nanometre regime along with the expected reduction in mass density.

High-temperature polyimide nanofoams for microelectronic applications

Abstract Foamed polyimides have been developed in order to obtain thin film dielectric layers with very low dielectric constants for use in microelectronic devices. In these systems the pore sizes are in the nanometer range, thus, the term ‘nanofoam’. The polyimide foams are prepared from block copolymers consisting of thermally stable and thermally labile blocks, the latter being the dispersed phase. Foam formation is effected by thermolysis of the thermally labile block, leaving pores of the size and shape corresponding to the initial copolymer morphology. Nanofoams prepared from a number of polyimides as matrix materials were investigated as well as from a number of thermally labile polymers. The foams were characterized by a variety of experiments including TEM, SAXS, WAXD, DMTA, density measurements, refractive index measurements and dielectric constant measurements. Thin film foams, with high thermal stability and low dielectric constants approaching 2.0, can be prepared using the copolymer/nanofoam approach.

Structures and dielectric properties of thin polyimide films with nano‐foam morphology

Thin polyimide films with dispersed nano‐foam morphology have been prepared for the purpose of obtaining low dielectric polymer insulators for microelectronic applications. They were obtained by utilizing micro phase‐separated triblock copolymers where the thermally stable polyimide matrix component was derived from pyromellitic dianhydride (PMDA) with 1,1‐bis(4‐aminophenyl)‐1‐phenyl‐2,2,2‐trifluoroethane (3F) and a thermally labile poly(propylene oxide)(PO) component comprised the outside block of the ABA triblock architecture. TEM studies show that the initial irregular nanoscale phase‐separated morphology of polyimide triblock copolymers are mostly maintained in the final nano‐foam films upon thermal decomposition of the dispersed PO component. The nano‐foam polyimide films exhibit significantly lower dielectric constants e′ (e.g., 2.3 at 19% porosity) as compared with e′≊2.9 for the homopolymer, as predicted by Maxwell–Garnett theory, with the nano‐pore structures remaining stable at 350 °C.

HighTg polyimide nanofoams derived from pyromellitic dianhydride and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane

New routes for the synthesis of high Tg thermally stable polymer foams with pore sizes in the nanometer regime have been developed. Foams were prepared by casting well-defined microphase-separated block copolymers comprised of a thermally stable block and a thermally labile material. At properly designed volume fractions the morphology provides a matrix of the thermally stable material with the thermally labile material as the dispersed phase. Upon thermal treatment, the thermally unstable block undergoes thermolysis generating pores, the size and shape of which are dictated by the initial copolymer morphology. Triblock copolymers comprised of a high Tg, amorphous polyimide matrix with poly(propylene oxide) as the thermally decomposable coblock, were prepared. The copolymer synthesis was conducted through the poly(amic acid) precursor and subsequent cyclodehydration to the polyimide by either thermal or chemical means. Dynamic mechanical analysis confirmed microphase separated morphologies for all copolymers, irrespective of the propylene oxide block lengths investigated. Upon decomposition of the thermally labile coblock, a 9–18% reduction in density was observed, consistent with the generation of a foam which was stable to 400°C.

Polyimide foams derived from a high Tg polyimide with grafted poly(α-methylstyrene)

Abstract A new route to high-Tg, thermally stable polyimide foams has been developed. Foams were prepared by casting microphase-separated graft copolymers comprising a thermally stable main chain, polyimide, and a thermally labile graft, poly(α-methylstyrene). The copolymer compositions were designed so that the thermally labile block would be the dispersed phase. This can unzip to its monomer upon heating, and the decomposition product diffuses out of the film, leaving pores embedded in a matrix of the thermally stable component. The copolymers were synthesized through either the poly(amic acid) precursor, followed by chemical cyclodehydration to the imide form, or the poly(amic alkyl ester) precursor followed by thermal imidization. The decomposition of the α-methylstyrene in the block copolymer was studied by thermogravimetric, dynamic mechanical and thermomechanical analyses. Mild decomposition conditions were required to avoid rapid depolymerization of the α-methylstyrene and excessive plasticization of the polyimide matrix. The foams showed pore sizes with diameters ranging from less than 20 nm to over 1 μm, depending upon the synthetic route employed, and the reduction in the mass density was generally consistent with the starting composition.

Polyimide Nanofoams For Low Dielectric Applications

Foamed polyimides have been developed in order to obtain thin film dielectric layers with very low dielectric constants for use in microelectronic devices. In these systems the pore sizes are in the nanometer range, thus, the term “nanofoam”. The polyimide foams are prepared from block copolymers consisting of thermally stable and thermally labile blocks, the latter being the dispersed phase. Foam formation is effected by thermolysis of the thermally labile block leaving pores the size and shape corresponding to the initial copolymer morphology. Nanofoams prepared from a number of polyimides as matrix materials, were investigated as well as a number of thermally labile polymers. The foams were characterized by a variety of experiments including, TEM, SAXS, WAXD, DMTA, density measurements, refractive index measurements and dielectric constant measurements. Thin film foams, with high thermal stability and dielectric constants approaching 2.0, can be prepared using the copolymer/nanofoam approach.

Electroluminescent devices based on cross-linked polymer blends

We report the electrical and optical properties of two-component blends of electron and hole transporting materials in single and bilayer structures for organic light emitting diode (OLED) applications. The materials considered were a blue-emitting bipolar transporting polyfluorene, poly(9,9-di-n-hexylfluorene) (DHF), and a hole-transporting material, poly-[4-nhexyltriphenylamine] (HTPA). We compare the steady state OLED performance, transport, and optical properties of devices and describe morphology studies of the polymer films based on cross-linkable (x) blends with the analogous non-cross-linkable blends. The cross-linkable blends exhibit highest efficiency at low concentrations of the hole transporting material. At these concentrations the single layer OLEDs reach efficiencies greater than 0.1%, and are higher than for single layer x-DHF or the binary non-cross-linkable blend by more than an order of magnitude. Bilayer structures with homogeneous x-HTPA as hole transport layer show efficiencies betwe...

Fluoro-alcohol materials with tailored interfacial properties for immersion lithography

Immersion lithography has placed a number of additional performance criteria on already stressed resist materials. Much work over the past few years has shown that controlling the water-resist interface is critical to enabling high scan rates (i.e. throughput) while minimizing film pulling and PAG extraction (i.e. defectivity). Protective topcoat polymers were developed to control the aforementioned interfacial properties and emerged as key enablers of 193 nm immersion lithography. Achieving the delicate balance between the low surface energies required for high water contact angles (generally achieved via the incorporation of fluorinated groups) and the base solubility required for topcoat removal is challenging. More recently, additional strategies using fluoropolymer materials to control the water-resist interface have been developed to afford topcoat-free resist systems. In our explorations of fluoroalcohol-based topcoat materials, we have discovered a number of structure-property relationships of which advantage can be taken to tailor the interfacial properties of these fluorinated materials. This paper will address the effect of structure on immersion specific properties such as water contact angle, aqueous base contact angle, and dissolution rate.